US6683011B2 - Process for forming hafnium oxide films - Google Patents

Process for forming hafnium oxide films Download PDF

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US6683011B2
US6683011B2 US09/992,173 US99217301A US6683011B2 US 6683011 B2 US6683011 B2 US 6683011B2 US 99217301 A US99217301 A US 99217301A US 6683011 B2 US6683011 B2 US 6683011B2
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substrate
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hafnium oxide
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Ryan C. Smith
Tiezhong Ma
Stephen A. Campbell
Wayne L. Gladfelter
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University of Minnesota
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604—Deposition from a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material

Definitions

  • This invention relates to forming a hafnium oxide film on a substrate by chemical vapor deposition.
  • MOSFETs metal oxide semiconductor field effect transistors
  • Examples include oxides of titanium, zirconium, and hafnium. These materials have higher dielectric constants than silicon dioxide, making it possible to achieve an equivalent capacitance using a thicker layer. The thicker layer, in turn, reduces leakage current.
  • the invention features a process for forming a hafnium oxide-containing film on a substrate such as silicon that includes introducing an anhydrous hafnium nitrate-containing precursor into a reactor containing the substrate, and converting the precursor into the hafnium oxide-containing film on the substrate by chemical vapor deposition.
  • the precursor may be introduced into the reactor in the form of a gas or a liquid. It may be used alone or in combination with a carrier gas such as nitrogen.
  • the hafnium nitrate may be used as a single source precursor or in the presence of an additional oxygen source such as oxygen (O 2 ), ozone (O 3 ), water (H 2 O) or hydrogen peroxide (H 2 O 2 ).
  • hafnium nitrate-containing precursor eliminates the need for a separate oxidizing agent such as oxygen.
  • a separate oxidizing agent such as oxygen.
  • the precursor is free of carbon, hydrogen, and halogen atoms, impurities in the final film are minimized.
  • FIG. 1 is a view of a HfO 2 film deposited on Si(100) obtained using cross-sectional transmission electron microscopy.
  • HfO 2 thin films of HfO 2 are grown using a precursor of anhydrous hafnium (IV) nitrate (“HN”).
  • HN may be synthesized using well known techniques, and is typically the reaction product of HfCl 4 and N 2 O 5 .
  • the reaction product is preferably purified by sublimation, and may be stored under an inert atmosphere.
  • the HN is initially loaded into a precursor vessel under an inert atmosphere.
  • the HN precursor vessel is then preferably heated to an appropriate temperature, typically about 80° C., and the chamber of the precursor vessel is maintained at below atmospheric pressure, typically at about 0.20 Torr.
  • the HN is deposited on a substrate to form a thin film using a chemical vapor deposition process.
  • Suitable substrates include Si(100) and the like.
  • the substrates are typically mounted on a heated susceptor situated in a low pressure reactor at a pressure of less than about 1 mTorr.
  • Suitable susceptors are made from molybdenum, and are heated temperatures between 300 and 500° C. during the deposition process.
  • Thin film growth rates typically range from about 2.5 to about 10.0 nm per minute.
  • the resulting deposited films are polycrystalline, monoclinic HfO 2 .
  • the HN may optionally be deposited with an inert carrier gas.
  • the carrier gas may vary widely, but nitrogen, preferably highly purified nitrogen, is suitable.
  • the HN precursor may be deposited in the presence of an additional oxygen source such as oxygen (O 2 ), ozone (O 3 ), water (H 2 O) or hydrogen peroxide (H 2 O 2 ).
  • the deposition of the HN was performed in a stainless steel low-pressure reactor, which consisted of a six-way cross equipped with 4.5 inch diameter Conflat flanges. Using only the mechanical pump, the base pressure of the reactor was ⁇ 1 mTorr. Two of the flanges were unused. One flange was equipped with a VitonTM o-ring sealed door for wafer loading. The precursor line enters the chamber through the top flange and the bottom flange is capped with fused silica window sealed to the flange knife-edge with a VitonTM o-ring. The Si(100) substrates were cleaned by standard procedures and placed onto a circular molybdenum susceptor (1 ⁇ 8-inch thick) situated at the center of the reactor.
  • the molybdenum susceptor was heated with a Variac-controlled, 1000 Watt, quartz halogen lamp located in a parabolic aluminum reflector and directed through the fused silica window.
  • the temperature of the susceptor was measured with a K-type thermocouple embedded one centimeter into the side of the susceptor.
  • the final flange was connected to the exhaust line that led through a Lindberg tube furnace set to 500° C. to destroy any unreacted precursor, a particle filter and, finally, to the mechanical pump .
  • a thermocouple gauge located between the six-way cross and the cracking furnace measured the reactor pressure.
  • the HN precursor vessel was heated to the desired temperature, 80° C., by Variac-controlled heating tape. High purity nitrogen was used as the carrier gas.
  • the flow of carrier gas was maintained at the desired flow, 20 sccm, using a mass flow controller.
  • the chamber pressure during deposition was 0.20 Torr.
  • the films were deposited at susceptor temperatures between 300 and 500° C. Under these conditions the observed growth rates ranged from 2.5 to 10.0 nm per minute.
  • the Rutherford backscattering spectrum was obtained on a spectrometer purchased from NEC that was equipped with a MAS 1700 end station.
  • the He + beam had an energy of 2.0 MeV, and the charge collected was typically 10 ⁇ C using a beam current of 15 nA.
  • Medium energy ion scattering data using a He + beam suggests that the ratio of O to metal in such high permittivity films is high by approximately 10%.
  • the stoichiometry of the as-deposited films ranged from HfO 2.2 to HfO 2.4 .
  • the observed ratio of O to Hf was higher for films that were deposited at lower temperatures.
  • Other metal oxides deposited using anhydrous metal nitrates were reported to contain excess oxygen, which could be removed by heating the films under an inert atmosphere.

Abstract

A process for forming a hafnium oxide-containing film on a substrate such as silicon that includes introducing an anhydrous hafnium nitrate-containing precursor into a reactor containing the substrate, and converting the precursor into the hafnium oxide-containing film on the substrate by chemical vapor deposition.

Description

This invention was made with government support under CHE-9616501 awarded by the National Science Foundation. The government has certain rights in the invention.
TECHNICAL FIELD
This invention relates to forming a hafnium oxide film on a substrate by chemical vapor deposition.
BACKGROUND
A number of materials have been proposed as replacements for silicon dioxide as the gate dielectric in metal oxide semiconductor field effect transistors (MOSFETs). Examples include oxides of titanium, zirconium, and hafnium. These materials have higher dielectric constants than silicon dioxide, making it possible to achieve an equivalent capacitance using a thicker layer. The thicker layer, in turn, reduces leakage current.
SUMMARY
In general, the invention features a process for forming a hafnium oxide-containing film on a substrate such as silicon that includes introducing an anhydrous hafnium nitrate-containing precursor into a reactor containing the substrate, and converting the precursor into the hafnium oxide-containing film on the substrate by chemical vapor deposition. The precursor may be introduced into the reactor in the form of a gas or a liquid. It may be used alone or in combination with a carrier gas such as nitrogen. The hafnium nitrate may be used as a single source precursor or in the presence of an additional oxygen source such as oxygen (O2), ozone (O3), water (H2O) or hydrogen peroxide (H2O2).
Using a hafnium nitrate-containing precursor eliminates the need for a separate oxidizing agent such as oxygen. In addition, because the precursor is free of carbon, hydrogen, and halogen atoms, impurities in the final film are minimized.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 is a view of a HfO2 film deposited on Si(100) obtained using cross-sectional transmission electron microscopy.
DETAILED DESCRIPTION
In the process of the invention, thin films of HfO2 are grown using a precursor of anhydrous hafnium (IV) nitrate (“HN”). The HN may be synthesized using well known techniques, and is typically the reaction product of HfCl4 and N2O5. The reaction product is preferably purified by sublimation, and may be stored under an inert atmosphere.
The HN is initially loaded into a precursor vessel under an inert atmosphere. The HN precursor vessel is then preferably heated to an appropriate temperature, typically about 80° C., and the chamber of the precursor vessel is maintained at below atmospheric pressure, typically at about 0.20 Torr.
The HN is deposited on a substrate to form a thin film using a chemical vapor deposition process. Suitable substrates include Si(100) and the like. The substrates are typically mounted on a heated susceptor situated in a low pressure reactor at a pressure of less than about 1 mTorr. Suitable susceptors are made from molybdenum, and are heated temperatures between 300 and 500° C. during the deposition process. Thin film growth rates typically range from about 2.5 to about 10.0 nm per minute. The resulting deposited films are polycrystalline, monoclinic HfO2.
The HN may optionally be deposited with an inert carrier gas. The carrier gas may vary widely, but nitrogen, preferably highly purified nitrogen, is suitable. Alternatively, the HN precursor may be deposited in the presence of an additional oxygen source such as oxygen (O2), ozone (O3), water (H2O) or hydrogen peroxide (H2O2).
EXAMPLE
The deposition of the HN was performed in a stainless steel low-pressure reactor, which consisted of a six-way cross equipped with 4.5 inch diameter Conflat flanges. Using only the mechanical pump, the base pressure of the reactor was <1 mTorr. Two of the flanges were unused. One flange was equipped with a Viton™ o-ring sealed door for wafer loading. The precursor line enters the chamber through the top flange and the bottom flange is capped with fused silica window sealed to the flange knife-edge with a Viton™ o-ring. The Si(100) substrates were cleaned by standard procedures and placed onto a circular molybdenum susceptor (⅛-inch thick) situated at the center of the reactor. The molybdenum susceptor was heated with a Variac-controlled, 1000 Watt, quartz halogen lamp located in a parabolic aluminum reflector and directed through the fused silica window. The temperature of the susceptor was measured with a K-type thermocouple embedded one centimeter into the side of the susceptor. The final flange was connected to the exhaust line that led through a Lindberg tube furnace set to 500° C. to destroy any unreacted precursor, a particle filter and, finally, to the mechanical pump . A thermocouple gauge located between the six-way cross and the cracking furnace measured the reactor pressure.
The HN precursor vessel was heated to the desired temperature, 80° C., by Variac-controlled heating tape. High purity nitrogen was used as the carrier gas. The flow of carrier gas was maintained at the desired flow, 20 sccm, using a mass flow controller. The chamber pressure during deposition was 0.20 Torr. The films were deposited at susceptor temperatures between 300 and 500° C. Under these conditions the observed growth rates ranged from 2.5 to 10.0 nm per minute.
Film crystallinity was studied using a Siemans D-5005 X-ray diffractometer and showed that films grown at 450° C. were polycrystalline, monoclinic HfO2. The observed preferential orientation was difficult to determine because of the close spacing and broadening of many of the reflections. The four strongest reflections occurred at 24.5, 28.6, 31.6, and 35.0°. The low angle peak could be attributed to either the 011 or 110 reflections, and the high angle peak could be due to the 002 or 200 reflections. The peaks at 28.6° and 31.6° could be uniquely assigned to the {overscore (1)} 11 and 111 reflections, respectively.
The Rutherford backscattering spectrum was obtained on a spectrometer purchased from NEC that was equipped with a MAS 1700 end station. The He+ beam had an energy of 2.0 MeV, and the charge collected was typically 10 μC using a beam current of 15 nA. Medium energy ion scattering data using a He+ beam suggests that the ratio of O to metal in such high permittivity films is high by approximately 10%. After adjusting the RBS data, the stoichiometry of the as-deposited films ranged from HfO2.2 to HfO2.4. The observed ratio of O to Hf was higher for films that were deposited at lower temperatures. Other metal oxides deposited using anhydrous metal nitrates were reported to contain excess oxygen, which could be removed by heating the films under an inert atmosphere.
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims (9)

What is claimed is:
1. A process for forming a film on a substrate, said process comprising introducing a precursor comprising anhydrous hafnium nitrate into a reactor containing the substrate, and converting the precursor into a film comprising hafnium oxide on the substrate by chemical vapor deposition.
2. A process according to claim 1 wherein the substrate comprises a silicon substrate.
3. A process according to claim 1 comprising introducing the precursor into the reactor in the form of a gas.
4. A process according to claim 1 comprising the precursor into the reactor in the form of a liquid.
5. A process according to claim 1 comprising forming the film at a rate ranging from about 2.5 to about 10 nm/min.
6. A process according to claim 1 further comprising introducing a carrier gas into the reactor with the precursor.
7. A process according to claim 1 further comprising introducing an additional oxygen source, into the reactor with the precursor.
8. The process of claim 7, wherein the additional oxygen source is selected from the group consisting of oxygen (O2), ozone (O3), water (H2O) and hydrogen peroxide (H2O2).
9. The process of claim 6, wherein the carrier gas is nitrogen.
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US20030045078A1 (en) * 2001-08-30 2003-03-06 Micron Technology, Inc. Highly reliable amorphous high-K gate oxide ZrO2
US20030157764A1 (en) * 2002-02-20 2003-08-21 Micron Technology, Inc. Evaporated LaA1O3 films for gate dielectrics
US20030207032A1 (en) * 2002-05-02 2003-11-06 Micron Technology, Inc. Methods, systems, and apparatus for atomic-layer deposition of aluminum oxides in integrated circuits
US20030207593A1 (en) * 2002-05-02 2003-11-06 Micron Technology, Inc. Atomic layer deposition and conversion
US20030227033A1 (en) * 2002-06-05 2003-12-11 Micron Technology, Inc. Atomic layer-deposited HfA1O3 films for gate dielectrics
US20040222476A1 (en) * 2002-01-17 2004-11-11 Micron Technology, Inc. Highly reliable amorphous high-k gate dielectric ZrOxNy
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US20060244082A1 (en) * 2005-04-28 2006-11-02 Micron Technology, Inc. Atomic layer desposition of a ruthenium layer to a lanthanide oxide dielectric layer
US7135369B2 (en) 2003-03-31 2006-11-14 Micron Technology, Inc. Atomic layer deposited ZrAlxOy dielectric layers including Zr4AlO9
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US8501563B2 (en) 2005-07-20 2013-08-06 Micron Technology, Inc. Devices with nanocrystals and methods of formation
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